CN101175794A - Method and apparatus for recovering (rubber-reinforced) styrenic resin composition - Google Patents
Method and apparatus for recovering (rubber-reinforced) styrenic resin composition Download PDFInfo
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- CN101175794A CN101175794A CNA200680016218XA CN200680016218A CN101175794A CN 101175794 A CN101175794 A CN 101175794A CN A200680016218X A CNA200680016218X A CN A200680016218XA CN 200680016218 A CN200680016218 A CN 200680016218A CN 101175794 A CN101175794 A CN 101175794A
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
- B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
- B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
A method by which various kinds of rubber-reinforced styrene resin compositions of good quality can be recovered in a small amount of energy in a satisfactory yield without posing a problem concerning environmental pollution. The method for recovering a (rubber-reinforced) styrene resin composition is characterized by conducting: a plastication step in which a styrene resin (A) is plasticated; a coagulation step in which a (rubber-reinforced) styrene resin latex (B) is mixed with a coagulant (C) to obtain a creamy substance (D); a mixing step in which the creamy substance (D) is fed to an extruder in which the styrene resin (A) which has undergone the plastication step is present, and they are mixed in the extruder to obtain a mixture (E); a draining step in which water is removed from the mixture (E) and discharged from the extruder; and a volatilization step in which volatile matters are removed from the mixture which has undergone the water removal and discharged from the extruder, the (rubber-reinforced) styrene resin composition being recovered from the extruder.
Description
Technical field
The present invention relates to from (rubber-reinforced) polystyrene resin latex (latex), reclaim the method for (rubber-reinforced) polystyrene resin composite.More particularly, the present invention relates to reclaim effectively the method for various types of high quality (rubber-reinforced) polystyrene resin composite, this method energy consumption is little, and can not cause that fine powder disperses, and does not produce a large amount of waste water, does not cause problem of environmental pollution.At this, " (rubber-reinforced) polystyrene resin latex " is meant rubber-reinforced polystyrene resin latex and/or polystyrene resin latex.Equally, " (rubber-reinforced) polystyrene resin composite " is meant rubber-reinforced polystyrene resin composite and/or polystyrene resin composite.
Background technology
Traditionally, the rubber-reinforced polyphenylacetylene combination that is used to make the ABS resin pellet is made by the following method: rubber-reinforced polystyrene resin latex coagulation is become slurry form, and clean, dewater, the rubber-reinforced polystyrene resin to pulp carries out drying then.
But above-mentioned traditional method has many problems, as cleaning and dehydration produces a large amount of waste water, and the energy input height, produces waste gas, produces in the drying process and the distribution fine powder.Consequently produce many secondary problems, low as productivity, antipollution cost height.
Consider the problems referred to above, proposed following method:
(1) solidifies → clean and dewater → squeeze-dewater and extrude and granulate
In the method, rubber-reinforced polystyrene resin latex coagulation pulp cleans and dehydration, is added in the forcing machine, and squeezing-dehydration in forcing machine is extruded and granulated from forcing machine.
The advantage of this method is that dry required energy must save, owing to there is not drying process, the exhausted air quantity of generation is very little.But when solidifying, need dehydration and cleaning process, still should be handled from a large amount of waste water of dehydration and cleaning process.Also have a problem to be, the resinous type that is fit to squeezing-dehydration is limited, so this method can not be used for all polytype resins.
(2) solidify in the forcing machine → dewater and drying → granulation (Fig. 3)
In the method, rubber-reinforced polystyrene resin latex is frozen into pulpous state in forcing machine 10X, dehydration and dry, and granulate (with reference to patent document 1).
Usually, molecular dimension resin dissolves viscosity big or that rubber components is many are very high.If use this method to process this resin, need very high power molten resin in forcing machine 10X, and molten resin is extruded from forcing machine 10X, owing to produce a large amount of heat, it is very high that resin temperature can become.Therefore, the shortcoming of this situation is the resin impact strength decreased of extruding from forcing machine 10X, perhaps tone deterioration.
Also have, when solidifying, resin is cleaned under the state of incomplete fusion, and the water former state that is used to clean is discharged, the resin particle that size is little is discharged by mechanical filter 61 with waste water, and the shortcoming of this situation is to need the large volume device that reclaims the resin particle that is discharged from.
Also have,, a lot of difficulties are being arranged aspect running efficiency and the machine maintenance because tube length/barrel dliameter (L/D) ratio of forcing machine 10X is very big.
And because process of setting all carries out in a forcing machine with the extrusion that is used for molten resin, it is impossible therefore two kinds of processes being selected best rotating speeds.In this case, except making forcing machine operation under the rotating speed of compromise, not have his choosing.Therefore, the shortcoming of this situation is that forcing machine can not have stable running condition, perhaps because the too high resin property deterioration that makes of rotating speed.
(3) solidify → clean and dewater → resin compound is plastified, squeezes-dewater and extrude, and granulate
In this method, rubber-reinforced polystyrene resin latex coagulation becomes pulpous state, cleans and dehydration, is recovered as wet powder.Then, this wet powder is added in the forcing machine plastifying polystyrene resin, mixes in forcing machine with the plasticizing polystyrene resin, and dehydration is to remove and drainage water, and devolatilization removes volatile matter, and granulate (with reference to patent document 2).
Similar with above-mentioned method (1), the advantage of this method is that dry required energy is saved, owing to there is not drying process, the exhausted air quantity of generation is very little.And, to compare with above-mentioned method (1), the advantage of this method is to squeeze-and dehydration has very high stability and degree of freedom.But this method still needs extra process of setting, dewaters separately and cleans, and its problem is that these extra process needs are discharged a large amount of water.
Patent document 1:USP 3993292
Patent document 2:JP 3597070 B
Summary of the invention
The technical problem to be solved in the present invention
The purpose of this invention is to provide a kind of method that reclaims all kinds high quality (rubber-reinforced) polystyrene resin composite effectively, this method energy input is little and can not cause that fine powder disperses, do not produce a large amount of waste water, do not cause problem of environmental pollution, and do not need to increase separately solidify, dehydration and cleaning process.
The scheme of dealing with problems
The present invention has following [1] to the feature described in [9]:
[1] feature 1:
The method of a kind of recovery (rubber-reinforced) polystyrene resin composite, it comprises:
Plasticizing process is used to plastify polystyrene resin (A);
Process of setting is used for (rubber-reinforced) polystyrene resin latex (B) and peptizer (C) are mixed, to obtain emulsus (creamy) material (D);
Mixing process is used for having finished the forcing machine of the polystyrene resin (A) of above-mentioned plasticizing process by above-mentioned milky substance (D) being offered wherein existence, and polystyrene resin (A) is mixed in forcing machine, obtains mixture (E);
Drainage procedure is used for discharging in above-mentioned forcing machine from said mixture (E) removal water and with water; With
Devolatilization (devolatilization) process is carried out devolatilization to said mixture, and volatile matter is discharged from above-mentioned forcing machine after removing water;
Wherein reclaim (rubber-reinforced) polystyrene resin composite from above-mentioned forcing machine by carrying out said process.
At this, " (rubber-reinforced) polystyrene resin latex (B) " is meant rubber-reinforced polystyrene resin latex (B) and/or polystyrene resin latex (B).Equally, " (rubber-reinforced) polystyrene resin composite " is meant rubber-reinforced polystyrene resin composite and/or polystyrene resin composite.The appellation of this mode is applied to hereinafter equally.
Milky substance (D) is meant (rubber-reinforced) polystyrene resin of pasty state, also can not be separated into solid and liquid (rubber-reinforced) polystyrene resin even also refer to leave standstill for a long time at ambient temperature (for example, one day).Owing to do not separate water outlet in the time of (rubber-reinforced) polystyrene resin latex (B) solidify out into milky substance (D), milky substance (D) can mix with good condition with the polystyrene resin that passes through plasticizing process (A).
[2] feature 2:
The method of recovery (rubber-reinforced) polystyrene resin composite described in feature 1,
Wherein above-mentioned plasticizing process upstream side at the supply position of above-mentioned milky substance (D) in above-mentioned extrusion machine carries out.
This recovery method that is used for reclaiming can be by the recovery system specific implementation of using Fig. 2 to exemplify.
[3] feature 3:
As the method for feature 1 described recovery (rubber-reinforced) polystyrene resin composite,
The above-mentioned plasticizing polystyrene resin (A) of wherein having finished above-mentioned plasticizing process in the plasticizing system provides to above-mentioned forcing machine at the upstream side of the supply position of above-mentioned milky substance (D).
This recovery method can be by using the recovery system specific implementation that is exemplified among Fig. 1.
[4] feature 4:
As the method for feature 1 to 3 recovery (rubber-reinforced) polystyrene resin composite described in any one,
Wherein dimension card (Vicat) softening temperature of above-mentioned (rubber-reinforced) polystyrene resin in latex (B) is T
m℃ the time, the temperature of solidification in the above-mentioned process of setting is (T
m-70) ℃ or higher.
If temperature of solidification is at (T
m-70) ℃, then in the mixture of polystyrene resin latex (B) and peptizer (C) a lot of non-emulsus parts will be arranged.Therefore, with have much can not with the polystyrene resin that passes through plasticizing process (A) with good condition blended part.
[5] feature 5:
As the method for feature 1 to 4 recovery (rubber-reinforced) polystyrene resin composite described in any one,
Wherein obtaining and the solids content concn of the milky substance (D) to the forcing machine is provided from above-mentioned process of setting is 15 to 40wt%.
If the solids content concn of milky substance (D) is lower than 15wt%, in the mixture of polystyrene resin latex (B) and peptizer (C) a lot of isolating water of non-lactous will be arranged.Therefore, with have much can not with the polystyrene resin that passes through plasticizing process (A) with good condition blended part.If the solids content concn of milky substance (D) is lower than 40wt%, then viscosity is too high can not be added to the mixture of polystyrene resin latex (B) and peptizer (C) in the polystyrene resin (A) that passes through plasticizing process.
[6] feature 6:
As the method for feature 1 to 4 recovery (rubber-reinforced) polystyrene resin composite described in any one,
Wherein in the supply position downstream side of above-mentioned milky substance (D) rinse water of 100 ℃ or higher temperature is provided to above-mentioned extrusion machine, the water in above-mentioned rinse water and the said mixture (E) is discharged in above-mentioned extrusion machine by twin shaft screw rod (screw) formula mechanical filter.
[7] feature 7:
As the method for feature 6 described recovery (rubber-reinforced) polystyrene resin composites,
Wherein behind above-mentioned mechanical filter, provide gas-liquid separating tank, in the control gas-liquid separating tank, in the gas phase partial pressure water is discharged.
[8] feature 8:
The system of a kind of recovery (rubber-reinforced) polystyrene resin composite, it comprises:
Main extruder;
Auxilliary forcing machine is used to plastify polystyrene resin; With
Coagulator;
Wherein above-mentioned forcing machine is equipped with first inlet that is used for auxilliary forcing machine in the position of upstream side, second inlet that is used for above-mentioned coagulator is housed in the downstream side of first inlet, and the water inlet that is used for rinse water is housed, is used for the escape orifice of rinse water and is used to remove the devolatilization mouth of volatile matter
Above-mentioned first inlet is connected with the discharge gate of auxilliary forcing machine,
Above-mentioned second inlet is connected with the discharge gate of coagulator,
The plastifying polystyrene resin provides to above-mentioned main extruder from the first above-mentioned inlet in above-mentioned auxilliary forcing machine, (rubber-reinforced) polystyrene resin of above-mentioned coagulator internal emulsification provides and mixes with polystyrene resin from above-mentioned second inlet, the mixture rinse water cleaning that provides from above-mentioned water inlet, mixture is melted in above-mentioned main extruder simultaneously, water after the cleaning is discharged from by mechanical filter from above-mentioned escape orifice, the water of mixture and discharge is devolatilization under negative pressure, and volatile matter is discharged from above-mentioned devolatilization mouth.
An example of this recovery system is presented among Fig. 1.
[9] feature 9:
As the system of feature 8 described recovery (rubber-reinforced) polystyrene resin composites,
Wherein behind above-mentioned mechanical filter, provide gas-liquid separating tank, and drought engine is provided, be used in the control gas-liquid separating tank, in the gas phase pressure partly water being discharged.
The invention effect
According to the method for feature 1 described recovery (rubber-reinforced) polystyrene resin composite, carry out plasticizing process, be used to plastify polystyrene resin (A); Process of setting is used for mixing (rubber-reinforced) polystyrene resin latex (B) and peptizer (C), to obtain milky substance (D); Mixing process is used for by milky substance (D) being offered wherein in the extrusion machine that has the polystyrene resin (A) of having finished above-mentioned plasticizing process, and will plastify polystyrene resin (A) and mix in forcing machine, obtains mixture (E); Drainage procedure is used for discharging in above-mentioned forcing machine from said mixture (E) removal water and with water; And devolatilization (devolatilization) process, behind above-mentioned removal water, mixture is carried out devolatilization, and volatile matter is discharged from above-mentioned forcing machine, to reclaim (rubber-reinforced) polystyrene resin composite from above-mentioned forcing machine.Therefore, even do not use large-scale device, also can reclaim polytype high quality (rubber-reinforced) polystyrene resin composite with very little energy input effectively, and not cause any problem of environmental pollution.
According to the method as feature 1 described recovery (rubber-reinforced) polystyrene resin composite described in the feature 2, above-mentioned plasticizing process upstream side at the supply position of above-mentioned milky substance (D) in above-mentioned extrusion machine carries out.Therefore, do not need to provide separately any device to come p-poly-phenyl ethenoid resin (A) to plastify.
According to the method described in the feature 3 as feature 1 described recovery (rubber-reinforced) polystyrene resin composite, above-mentioned plasticizing process carries out in the plasticizing system, and plasticizing polystyrene resin (A) provides to above-mentioned forcing machine from the upstream side of the supply position of above-mentioned milky substance (D).Therefore, the plasticizing of polystyrene resin (A) and above-mentioned plasticising polystyrene (A) and slurry (milky substance) (D) mixed and the mixing process that melts can independently carried out in the system by setting top condition respectively.Owing to this reason, can reclaim more eurypalynous high quality (rubber-reinforced) polystyrene resin composite.
According to the method described in the feature 4, when the vicat softening temperature of above-mentioned (rubber-reinforced) polystyrene resin in latex (B) is T as feature 1 to 3 any one described recovery (rubber-reinforced) polystyrene resin composite
m℃ the time, the temperature of solidification in the above-mentioned process of setting is (T
m-70) ℃ or higher.Therefore, plasticizing polystyrene resin (A) and milky substance (D) can mix well.
According to described in the feature 5 as the method for feature 1 to 4 any one described recovery (rubber-reinforced) polystyrene resin composite, obtaining and the solids content concn scope of the milky substance (D) to the forcing machine is provided from above-mentioned process of setting is 15 to 40wt%.Therefore, plasticizing polystyrene resin (A) and milky substance (D) can mix well.
According to described in the feature 6 as the method for feature 1 to 4 recovery (rubber-reinforced) polystyrene resin composite described in any one, rinse water in the supply position downstream side of above-mentioned milky substance (D) with 100 ℃ or higher temperature provides to above-mentioned extrusion machine, and the water in above-mentioned rinse water and the said mixture (E) is discharged in above-mentioned extrusion machine by double-shaft spiral (screw) formula mechanical filter.Therefore, can be with the removal well from the material of the mixing of plasticizing polystyrene resin (A) and milky substance (D) and fusing of the water of resinous composition hardly.
According to described in the feature 7 as the method for feature 6 described recovery (rubber-reinforced) polystyrene resin composites, behind above-mentioned mechanical filter, provide gas-liquid separating tank, in the control gas-liquid separating tank, water is discharged the gas phase partial pressure time.Therefore, when resin and water were separated from one another in forcing machine, water can separate as liquid under pressure under the unvaporized situation.
According to the system of recovery (rubber-reinforced) polystyrene resin composite described in the feature 8, can be provided for realizing the object lesson of the system of the recovery method described in the feature 3 (with the feature 4 to 6 that is subordinated to feature 3).
According to the system of recovery (rubber-reinforced) polystyrene resin composite described in the feature 9, can be provided for realizing the object lesson of the system of the recovery method described in the feature 7.
Description of drawings
Fig. 1 is the explanation synoptic diagram that is used to make according to the particulate recovery system of the embodiment of feature 3;
Fig. 2 is the explanation synoptic diagram according to the recovery system of feature 2 of the present invention;
Fig. 3 is the explanation synoptic diagram of particulate (tradition) recovery system that is used to make comparative example;
Fig. 4 is the explanation synoptic diagram of Fig. 1 system, wherein schematic representations auxilliary forcing machine 20, coagulator 30 and main extruder 10, the parts before the auxilliary forcing machine 20, the parts before the coagulator 30 and the parts after the mechanical filter are concealed.
The explanation of numeral
10---is according to the main extruder of recovery system of the present invention
10B---is according to the main extruder of recovery system of the present invention
The forcing machine of 10X---tradition recovery system
20---assists forcing machine
The 30---coagulator
Industrial applicability
1. raw material and condition:
(a) polystyrene resin (A)
As polystyrene resin (A), can use the polymer of similar animi resin, such as polystyrene, styrene-methyl methacrylate (MS resin), SAN (AS resin), styrene-acrylonitrile-methacrylate (MAS resin) and styrene-acrylonitrile-N-phenyl maleimide; With the polymer of similar resin, such as the SAN (AAS resin) of acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-ethene-polypropylene rubber-styrene resin (AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), HTPS resin (HIPS resin) and acrylic rubber sex change.
When using the AS resin as polystyrene resin (A), with when being used for regulating the matrix body of product characteristics, the temperature range that plastifies the AS resin is 100 to 200 ℃, preferred 110 to 160 ℃.
(b) (rubber-reinforced) polystyrene resin latex (B)
As (rubber-reinforced) polystyrene resin latex (B), can use the following polymers latex that obtains by emulsion polymerisation: can use the polymer of rubber like, such as SBR styrene butadiene rubbers (SBR); The polymer of similar animi resin is such as polystyrene, styrene-methyl methacrylate (MS resin), SAN (AS resin), styrene-acrylonitrile-methacrylate (MAS resin) and styrene-acrylonitrile-N-phenylmaleimide; With the polymer of similar resin, such as the SAN (AAS resin) of SAN (AES resin), methyl methacrylate-butadiene styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), HTPS resin (HIPS resin) and the acrylic rubber sex change of acrylonitrile-butadiene-styrene copolymer (ABS resin), ethene-polypropylene sex change.
Method according to recovery of the present invention (rubber-reinforced) polystyrene resin composite can be used for hybrid resin latex, this resin latex by emulsion polymerization or by with resin and be used for regulating of will merging or the resin that improves mechanical performance, outward appearance and other performances again emulsification obtain. Specifically, as polystyrene resin (A) or (rubber-reinforced) polystyrene resin latex (B), can use AS resin, ABS resin latex, MAS resin latex, MABS resin latex, AS resin or ASA resin latex, AS resin or AES resin latex, AS resin or AS resin latex etc.
When using ABS resin latex as (rubber-reinforced) polystyrene resin latex (B), resin concentration should be preferably in 25 to 45wt% scope, and the addition of coagulating agent (C) should preferable range be 1 to 10 weight portion of 100 weight portion ABS resins. Therefore, by with the mixing of (rubber-reinforced) polystyrene resin latex (B) of these ratios and coagulating agent (C) with solidify, the solids content concn of milky substance (D) is adjustable in 15 to 40wt% the scope, preferred 20 to 40wt%, and more preferably 25 to 35wt%. If the solids content concn of milky substance (D) is lower than 15wt%, the water that separates that a lot of non-emulsus then will be arranged in the mixture of (rubber-reinforced) polystyrene resin latex (B) and coagulating agent (C), therefore, the part that can not well mix with the polystyrene resin that passes through above-mentioned plasticizing process (A) will be had a lot. If the solids content concn of milky substance (D) is higher than 40wt%, then viscosity is very high, so that be difficult to the mixture of (rubber-reinforced) polystyrene resin latex (B) and coagulating agent (C) is added in the polystyrene resin (A) that passes through plasticizing process. When the solids content concn of milky substance (D) is in 20 to 40wt% preferable range, in shape with mixing of the polystyrene resin that passes through plasticizing process (A). When in the more preferably scope of solids content concn 25 to 35wt% of milky substance (D), be in better state with mixing of the polystyrene resin that passes through plasticizing process (A).
(c) coagulating agent (C)
As coagulating agent (C), can use the coagulating agent that is generally used for solidified polymeric latex. For example, can use inorganic acid, example hydrochloric acid, sulfuric acid and nitric acid; Organic acid is such as acetic acid and formic acid; With these sour slaines. For example, as slaine, can use inorganic salts, such as calcium chloride, aluminium chloride, aluminum sulfate and magnesium sulfate; And organic salt, such as calcium acetate and magnesium acetate. Although slaine can be used as solid or is dissolved in the water or otherwise use, preferably, slaine should use as 3 to 25wt% the aqueous solution. Above-mentioned coagulating agent can use as one type of coagulating agent independently, perhaps is combined with other coagulating agents of two or more types.
By the solids content concn of consideration (rubber-reinforced) polystyrene resin latex (B) and the flocculation value of (rubber-reinforced) polystyrene resin, determine the addition of coagulating agent (C). Usually, the addition of coagulating agent (C) is 1 to 10 weight portion or preferred 1 to 8 weight portion in 100 weight portions (rubber-reinforced) polystyrene resin. If the addition of coagulating agent (C) is less than 1 weight portion, then (rubber-reinforced) polystyrene resin (B) can not fully solidify. In this case, as mentioned above, have a lot of non-emulsus parts in the mixture of (rubber-reinforced) polystyrene resin latex (B) and coagulating agent (C). Therefore, have much the part that can not well mix with the polystyrene resin that passes through plasticizing process (A). If the addition of coagulating agent (C) surpasses 10 weight portions, then owing to surpass the necessary amounts of coagulating agent (C), can cause waste. In addition, as mentioned above, viscosity will be too high, so that be difficult to the mixture of (rubber-reinforced) polystyrene resin latex (B) and coagulating agent (C) is added in the polystyrene resin (A) that passes through plasticizing process. At this, above-mentioned " flocculation value " refers to leave standstill one section special time when (rubber-reinforced) polystyrene resin latex (B) coagulating agent (C) different with solids content concn that will have specific solids content concn mixes, when confirming precipitation occurs, precipitating least concentration (mixed concentration).
(d) setting temperature
When the vicat softening temperature of (rubber-reinforced) polystyrene resin in latex (B) is Tm℃ the time, be (T by the setting temperature of (rubber-reinforced) polystyrene resin latex (B) and coagulating agent (C) being mixed available milky substance (D)m-70) ℃ or higher. If setting temperature is lower than (Tm-70) ℃, because the material that solidifies can not be solidified into pasty state, but remain the low liquid of viscosity, the material that solidifies can not mix with the polystyrene resin that passes through plasticizing process (A). The upper limit of setting temperature should be determined that it is about 90 ℃ by the stringent condition of stable heating by (rubber-reinforced) polystyrene resin latex (B).
When (rubber-reinforced) polystyrene resin latex (B) and coagulating agent (C) mixing, and be set in and become together milky substance (D), when then milky substance (D) being provided interior to the extruder that contains the polystyrene resin (A) that passes through plasticizing process, when the vicat softening temperature of polystyrene resin (A) is Tn ℃, by the milky substance (D) that under (Tn-70) ℃ or higher temperature, solidifies and the Tn ℃ of combining proportion to the polystyrene resin that passes through plasticizing process (A) of (Tn+100) ℃, determine the temperature of mixture. But preferably this temperature should not be lower than Tn ℃.
(e) rinse water
Will be through the polystyrene resin (A) of plasticizing process and mixed process that milky substance (D) mixes in, mix and the resin of fusing can provide steam with the high-temperature water of 100 ℃ under the high pressure or higher temperature or 100 to 200 ℃ as rinse water, be used for cleaning the polymerization auxiliary material, such as emulsifying agent, coagulating agent (D) etc. Also can be arranged to water is separated from mixture (E), and discharge in the drainage procedure of back with above-mentioned rinse water. When the water that high temperature, high pressure are provided as mentioned above or steam, the coagulated substance in the milky substance (D) can obtain heating, and its effect can promote plastication. The supply of this high-temperature high pressure water or steam (quality) should be preferably 2 times of resin or more still less. The temperature of steam preferably scope is 110 to 180 ℃, should should scope be 120 to 160 ℃ preferably. If the temperature of steam is lower than 110 ℃, because heat energy very little, then has the problem that resin can not fully plastify. If the temperature of steam is higher than 180 ℃, because steam pressure is too high, then have the problem that needs high-pressure installation and difficult treatment.
(f) mixed proportion
Mixed proportion as for polystyrene resin (A) and (rubber-reinforced) polystyrene resin latex (B), when (B) was rubber-reinforced polystyrene resin latex, the rubber components content after mixing in the resin combination should be preferably in 10 to 35wt% scope. As (B) when not containing rubber components, the content of (B) component should be preferably in 10 to 80wt% scope in the resin combination after mixing.
2. recovery system
By using Fig. 1,2 and 4 and with reference to Fig. 3, describe and implement recovery system of the present invention, yet the present invention is not limited to Fig. 1,2 and 4. In addition, in this was described, the AS resin will be as the example of polystyrene resin (A), and ABS resin latex will be as the example of rubber-reinforced polystyrene resin latex (B), yet embodiment is not limited to these resins.
The recovery system of Fig. 1
At first, the recovery system of description as showing among Fig. 1. This recovery system is for the embodiment 1-3 that describes later. This recovery system is equipped with main extruder 10, be used for the auxiliary extruder 20 of plasticizing polystyrene resin (A) and be used for rubber-reinforced polystyrene resin latex (B) and coagulating agent (C) are mixed into together the coagulator 30 of emulsus.
The first inlet 101 is connected with the transmission mouth (delivery port) of auxiliary extruder 20, and the second inlet 102 is connected with the transmission mouth of coagulator 30. Inlet 103 is connected with the supply line of rinse water (or steam), and discharge outlet 104 is connected with mechanical filter 41, and devolatilization mouth 105a and 105b and vacuum air pump (ventilating opening) 43 are connected with 43. Incidentally, above-mentioned discharge outlet 104 and mechanical filter all can have a plurality of separately, that is, can be arranged with a plurality of along the resin direction of advance in that main extruder 10 is interior. The above-mentioned devolatilization mouth 105a that shows among Fig. 1 and 105b and vacuum air pump 43 and 43 but also can be respectively in 3 or more position and device respectively in two positions and device.
Provide AS resin and additive in auxiliary extruder, this resin is polystyrene resin (A), and AS resin and additive are melted (plasticizing) therein. The matrix body of this plastifying fusion state or semi-molten state (matrix body) provides to main extruder 10 from inlet 101.
As shown in Figure 4, under the pressure of pump 303, in coagulator 30, sequentially provide ABS resin latex (=rubber-reinforced polystyrene latex (B)), wherein ABS resin latex provides to system from the outside, and in reactor 301 internal emulsifications and polymerization, and temporary transient drainage is to tank 302. In addition, in coagulator 30, sequentially provide coagulating agent (C).
Provide ABS resin latex and coagulating agent to the coagulator 30 to be made into emulsus, be pushed forward in cylinder by screw rod simultaneously. This milky substance is pushed out under the pressure of said pump 303 in the main extruder 10, that is, contact and mix with plasticizing AS resin (=polystyrene resin (A)).
By this way, AS resin (=polystyrene resin (A)) is being mixed together into molten condition with the ABS resin latex that solidifies (=milky substance (D)) in main extruder 10. Mixture from from inlet 103 to this molten condition provides the rinse water (or steam) of HTHP. This rinse water is discharged from from discharge outlet 104 by the water that mechanical filter 41 comprises in above-mentioned milky substance (D).
As shown in Figure 4, after mechanical filter 41, has knockout drum 411. Provide control valve 412a in the drainage pipeline of this knockout drum 41 1. The opening/closing degree of control valve 412a, namely drainage rates is controlled by horizontal controller 412, so that the fluid level in the knockout drum 411 can remain on specified level. In addition, provide control valve 415a in the discharge duct of knockout drum 411. The opening/closing degree of control valve 415a, namely deflation rate is controlled by horizontal controller 415, so that the pressure of the part of the gas phase in the knockout drum 411 can remain on the specified pressure. At this, the specified pressure that gas phase part will keep is such as downforce: water is isolated and by the pressure that mechanical filter 41 is removed in the main extruder 10 remain on water the vapour pressure under this temperature or on. This pressure energy separates water with liquid condition in nonvolatile situation. Incidentally, from the water of discharging by control valve 412a, reclaim the leakage resin of trace by mechanical filter 413. The resin of these leakages is back to the entrance of coagulator 30 through fine powder recycling can 414 by pump. In addition, will remove by mechanical filter 413 the filtrate discharge of resin.
With above-mentioned rinse water and the mixture of the water that comprises in the milky substance (D) of removing in this way taken away by vacuum by vacuum air pump 43, thereby volatile materials is discharged from devolatilization mouth 105a and 105b.
Mixture dehydrated, again devolatilization is discharged from the back(ing) board that is positioned at main extruder 10 front ends with continuous casting fluidised form (strand state) by this way, in cooling tank 71 interior coolings, is cut into pellet (pellet) by cutting machine 72. From pellet, remove fine foreign substance by vibratory sieve 73. Then, reclaim pellet by cyclone separator.
The recovery system of Fig. 2
Secondly, will the recovery system shown in Fig. 2 be described. Because the recovery system of Fig. 2 is almost identical with the recovery system of Fig. 1, therefore identical part will be with identical numerical reference, and will be for different part descriptions. Incidentally, each mechanical device in the coagulator shown in Fig. 4 30 and the mechanical filter 41 also is the device in the recovery system of Fig. 1.
The auxiliary extruder 20 of the recovery system default map 1 of Fig. 2, namely the structure of system is simplified. According to the recovery system of Fig. 2, matrix body (AS resin and additive) plastifies in the highest region territory of main extruder 10B, provides the inlet 102 of coagulator 30 in the existing zone of the matrix body of this plasticizing. Because adopt this structure, the tube length of the main extruder 10B of Fig. 2 is greater than the tube length of the main extruder 10 of Fig. 1.
The recovery system of Fig. 3 (recovery system of comparative example)
To describe briefly the recovery system of Fig. 3, this system can not realize that according to recovery method of the present invention, this system will be hereinafter as a comparative example.
According to the recovery system of Fig. 3, main extruder 10 is equipped with a plurality of inlet (not shown) and a plurality of discharge outlet (not shown) for the discharging rinse water be used to cleaning steam is provided, but also a plurality of mechanical filters 61 and vacuum air pump 43 are housed.
According to the recovery system of Fig. 3, raw material (ABS resin latex and coagulating agent) is supplied in the main extruder 10X, plasticising when pushing ahead is provided with cleaning steam, and cleans with it. The cleaning steam of condensation is discharged from, devolatilization is also discharged. When raw material fusing and cleaning, rinse water is devolatilization in same cylinder, therefore can not be the rotating speed of these process choosing the bests. Because this defective can not be controlled each process best, the quality of the resin that discharges is also defective. For example, the problem that may exist has, and for example, the temperature of molten resin is too high, and resin degraded (molecule cutting (molecular cut)) is accelerated, and MFR raises too many, and impact strength reduces, and bL (yellow colors) increases. Another the complex nature of the problem is to regulate the amount of rubber components in the later stage process, because can not adjust by matrix body.
Embodiment
Hereinafter, the present invention will be described particularly with reference to some embodiments, although the present invention is not limited to these embodiments.In the description of these embodiments, unless otherwise noted, " part " and " % " is all based on quality.The evaluation of estimate of mentioning in the embodiment is the numerical value according to measurement as described below:
[evaluation method]
(1)MFR：
According to ISO1133, under 220 ℃ temperature, under the load of 98N, measure.
(2) summer is than shock strength (Charpy impact strength):
Go up the resin granular material that forms acquisition at injector (Niigata Engineering NN30B), measure shock strength according to ISO179.
(3) tone:
On above-mentioned injector, form the specimen of 3.2 * 40 * 80mm, use colour-difference meter (Gardner TCS-II (light source C, reflection method d-8)) to measure tone.
[raw material]
(1) polystyrene resin (A):
Use SANREX SAN-C (Techno Polymer) (melt flow rate (MFR): 25g/10min (220 ℃, 98N), AN content: 26%).
(2) (rubber-reinforced) polystyrene resin latex (B):
B-1：
Use known method to make ABS resin latex for 13.5 parts with 50 parts of butadiene rubber latex (solids content equivalent), 36.5 parts of vinylbenzene and vinyl cyanide.The solids content of the ABS resin latex of making is 33%, and the rubber content of its resin is 50%, and the AN% of its matrix part (acetone soluble part) is 27%, and its limiting viscosity is 0.41dl/g, and its percentage of grafting is 55%.B-2：
Use known method with 16.2 parts of 40 parts of butadiene rubber latex (solids content equivalent), 43.8 parts of vinylbenzene and vinyl cyanide by making ABS resin latex.The solids content of the ABS resin latex of making is 34.5%, and the rubber content of its resin is 40%, and the AN% of its matrix part (acetone soluble part) is 27%, and its limiting viscosity is 0.45 dl/g, and its percentage of grafting is 62%.
[embodiment 1-3, comparative example 1 and 2]
Use the pellet of the recovery system manufacturing embodiment 1-3 of Fig. 1.The details of the composition of embodiment 1-3 and manufacturing process (as operational condition) is presented in the table 1.
By using the recovery system of Fig. 3, make the pellet of comparative example 1 and 2.The details of the composition of comparing embodiment and manufacturing process (as operational condition) is presented in the table 2.
And, the pellet of comparative example 1 and 2 is mixed with the AS pellet, and in the single shaft forcing machine, mediate and granulate, thereby make comparative example 11,12 identical and 21 pellet, to be used for the evaluation of physicals, wherein with the rubber content of embodiment 1-3
The pellet of comparative example 11 has identical rubber content with embodiment 1;
The pellet of comparative example 12 has identical rubber content with embodiment 2; With
The pellet of comparative example 21 has identical rubber content with embodiment 3.
Estimate the foregoing description 1,2 and 3 and the quality of every kind of pellet of comparative example 11,12 and 21.Evaluation result is presented in the table 3.
[evaluation result]
1) is clear that from table 1 and 2 that comparative example 1 and 2 band water-resin (water entrainingresin) yield are greater than embodiment 1,2 and 3.
2) find out from table 1 and 2 that for comparative example 11,12 and 21, because the temperature of front end resin increases, as shown in table 3, MFR increases, the summer descends than shock strength, and for tone, yellow colors increases, and whiteness descends.
Incidentally, make the embodiment pellet by the recovery system of using Fig. 2, and compare with the contrast pellet of making in the same manner as mentioned above, the result of acquisition much at one.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |||
| (A) polystyrene resin | Feeding rate [kg/hr] | 130 | 160 | 115 | |
| (B) (rubber-reinforced) polystyrene resin latex | Type | B-1 | B-2 | B-3 | |
| Solids content concn [wt%] | 33 | 33 | 34.5 | ||
| The rubber components of resin [wt%] | 50 | 50 | 40 | ||
| Vicat softening temperature (℃) | 101 | 101 | 106 | ||
| Feeding rate [L/hr] (solids content [kg/hr]) | 200(66) | 150(49.5) | 180(62.1) | ||
| (C) peptizer | Magnesium sulfate solution (8wt%) | Feeding rate [L/hr] | 17 | 13 | 16 |
| The high temperature rinse water | High temperature (120-130 ℃) high pressure water | Feeding rate [L/hr] | 50 | 50 | 50 |
| The content [wt%] of rubber components in the final ABS composition | 16.8 | 12 | 14 | ||
| Coagulator | Internal temperature [℃] | 45 | 48 | 55 | |
| Auxilliary forcing machine | The barrel heater temperature [℃] | 150 to 200 | 150 to 200 | 150 to 200 | |
| The front end resin temperature [℃] | 190 | 185 | 200 | ||
| Main extruder | The barrel heater temperature [℃] | 150 to 200 | 150 to 200 | 150 to 200 | |
| Free-water recovery volume [L/hr] | 155 | 132 | 150 | ||
| Band water-resin yield [kg/hr] | 0.3 to 0.8 | 0.3 to 0.5 | 0.5 to 0.7 | ||
| The front end resin temperature [℃] | 245 | 235 | 238 | ||
[table 2]
| Comparative example 1 | Comparative example 2 | |||
| (B) (rubber-reinforced) polystyrene resin latex | Type | B-1 | B-2 | |
| Solids content concn [wt%] | 33 | 34.5 | ||
| The rubber components of resin [wt%] | 50 | 40 | ||
| Vicat softening temperature (℃) | 101 | 106 | ||
| Feeding rate [L/hr] (solids content [kg/hr]) | 300(99) | 360(124.2) | ||
| (C) peptizer | Magnesium sulfate solution (8wt%) | Feeding rate [L/hr] | 25 | 30 |
| High temperature rinse water 1 | High temperature (120-130 ℃), high pressure water | Feeding rate [L/hr] | 50 | 50 |
| High temperature rinse water 2 | High temperature (120-130 ℃), high pressure water | Feeding rate [L/hr] | 30 | 30 |
| Main extruder | The barrel heater temperature [℃] | 150 to 200 | 150 to 200 | |
| Two filter free-water recovery volumes [L/hr] | 285 | 327 | ||
| Band water-resin yield [kg/hr] | 15 | 20 | ||
| The front end resin temperature [℃] | 290 | 283 | ||
[table 3]
| Assessment item | Unit | Result (EB: embodiment, CE: comparative example) | |||||
| EB1 | EB2 | EB3 | CE11 | CE12 | CE21 | ||
| MFR(220℃ *98N) | g/10min | 12 | 37 | 17 | 17.5 | 48.0 | 21.5 |
| Summer is compared shock strength | KJ/m | 28 | 18 | 20 | 15.3 | 11.5 | 15.2 |
| Tone | |||||||
| L | 86.0 | 87.0 | 85.3 | 80.5 | 82.1 | 82.1 | |
| aL | -2.7 | -3.6 | -3.3 | -1.8 | -2.4 | -2.1 | |
| bL | 4.5 | 1.5 | 5.5 | 14.5 | 9.7 | 10.2 | |
| W | 58.5 | 59.1 | 58.2 | 51.5 | 52.3 | 54.3 | |
Possible industrial application
The present invention can be used for effectively making polytype high-quality (rubber-reinforced) polystyrene resin composite with very little energy input, and does not cause that fine powder scatters, and does not produce a large amount of waste water, does not cause problem of environmental pollution.
Claims (9)
1. the method for a recovery (rubber-reinforced) polystyrene resin composite, it comprises:
Plasticizing process is used to plastify polystyrene resin (A);
Process of setting is used for (rubber-reinforced) polystyrene resin latex (B) and peptizer (C) are mixed, to obtain milky substance (D);
Mixing process is used for by described milky substance (D) being offered wherein in the forcing machine that has the polystyrene resin (A) of having finished described plasticizing process, and described polystyrene resin (A) is mixed in described forcing machine, obtains mixture (E);
Drainage procedure is used for discharging in described forcing machine from described mixture (E) removal water and with water; With
The devolatilization process is carried out devolatilization to described mixture, and volatile matter is discharged from described forcing machine after removing water;
Wherein reclaim (rubber-reinforced) polystyrene resin composite from described forcing machine by carrying out said process.
2. the method for recovery according to claim 1 (rubber-reinforced) polystyrene resin composite,
Wherein said plasticizing process upstream side at the supply position of described milky substance (D) in described extrusion machine carries out.
3. the method for recovery according to claim 1 (rubber-reinforced) polystyrene resin composite,
The described plasticizing polystyrene resin (A) of wherein having finished described plasticizing process in the plasticizing system provides to described forcing machine at the upstream side of the supply position of described milky substance (D).
4. according to the method for any described recovery (rubber-reinforced) polystyrene resin composite among the claim 1-3,
Wherein the vicat softening temperature of described (rubber-reinforced) polystyrene resin in described latex (B) is T
m℃ the time, the temperature of solidification in the described process of setting is (T
m-70) ℃ or higher.
5. according to the method for any described recovery (rubber-reinforced) polystyrene resin composite among the claim 1-4,
Wherein obtaining and the solids content concn of the milky substance (D) to the forcing machine is provided from described process of setting is 15 to 40wt%.
6. according to the method for any described recovery (rubber-reinforced) polystyrene resin composite among the claim 1-4,
Wherein in the supply position downstream side of described milky substance (D) rinse water of 100 ℃ or higher temperature is provided to described extrusion machine, the water in described rinse water and the described mixture (E) is discharged in described extrusion machine by twin shaft screw mechanical filter.
7. the method for recovery according to claim 6 (rubber-reinforced) polystyrene resin composite,
Wherein behind described mechanical filter, provide gas-liquid separating tank, in the control gas-liquid separating tank, in the gas phase partial pressure water is discharged.
8. the system of a recovery (rubber-reinforced) polystyrene resin composite, it comprises:
Main extruder;
Auxilliary forcing machine is used to plastify polystyrene resin; With
Coagulator;
Wherein said forcing machine is equipped with first inlet that is used for auxilliary forcing machine in the position of upstream side, second inlet that is used for described coagulator is housed in the downstream side of first inlet, and the water inlet that is used for rinse water is housed, is used for the escape orifice of rinse water and is used to remove the devolatilization mouth of volatile matter
Described first inlet is connected with the discharge gate of described auxilliary forcing machine,
Described second inlet is connected with the discharge gate of described coagulator,
The plastifying polystyrene resin provides to described main extruder from described first inlet in described auxilliary forcing machine, (rubber-reinforced) polystyrene resin of above-mentioned coagulator internal emulsification provides and mixes with polystyrene resin from described second inlet, the rinse water cleaning that provides from described water inlet of described mixture, described mixture is melted in described main extruder simultaneously, water after the cleaning is discharged from by mechanical filter from described escape orifice, the water of mixture and discharge is devolatilization under negative pressure, and volatile matter is discharged from described devolatilization mouth.
9. the system of recovery according to claim 8 (rubber-reinforced) polystyrene resin composite,
Wherein behind described mechanical filter, provide gas-liquid separating tank, and drought engine is provided, be used in the control gas-liquid separating tank, in the gas phase pressure partly water being discharged.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005072819 | 2005-03-15 | ||
| JP072819/2005 | 2005-03-15 | ||
| PCT/JP2006/304931 WO2006098287A1 (en) | 2005-03-15 | 2006-03-13 | Method and apparatus for recovering (rubber-reinforced) styrene resin composition |
Publications (2)
| Publication Number | Publication Date |
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| CN101175794A true CN101175794A (en) | 2008-05-07 |
| CN101175794B CN101175794B (en) | 2011-02-09 |
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| CN200680016218XA Expired - Fee Related CN101175794B (en) | 2005-03-15 | 2006-03-13 | Method and apparatus for recovering (rubber-reinforced) styrenic resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5064701B2 (en) |
| KR (1) | KR101279244B1 (en) |
| CN (1) | CN101175794B (en) |
| WO (1) | WO2006098287A1 (en) |
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|---|---|---|---|---|
| CN102152459A (en) * | 2009-12-23 | 2011-08-17 | 固特异轮胎和橡胶公司 | Continuous mixing system and apparatus |
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| KR101157299B1 (en) * | 2008-02-01 | 2012-06-15 | 주식회사 엘지화학 | Device of preparing polymer slurry with high solid contents and method of preparing using the same |
| JP2014512994A (en) * | 2011-05-13 | 2014-05-29 | エヌエフエム ウェルディング エンジニーアズ，インコーポレイテッド | Improved dewatering machine and dewatering method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5937021B2 (en) * | 1980-03-19 | 1984-09-07 | 電気化学工業株式会社 | ABS resin manufacturing method |
| JPH0742392B2 (en) * | 1986-01-07 | 1995-05-10 | 東芝機械株式会社 | ABS resin manufacturing method and apparatus |
| WO1998013412A1 (en) * | 1996-09-26 | 1998-04-02 | Basf Aktiengesellschaft | Process for producing thermoplastics |
| JP3597070B2 (en) * | 1999-01-20 | 2004-12-02 | 東芝機械株式会社 | Apparatus and method for producing impact-resistant thermoplastic resin |
| CN1133689C (en) * | 2000-03-22 | 2004-01-07 | 范宸天 | Method of foaming polystyrene to produce polystyrene products |
| DE10318109A1 (en) * | 2003-04-22 | 2004-11-11 | Bayer Ag | Method and device for producing elastomer-modified thermoplastics |
-
2006
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- 2006-03-13 KR KR1020077023421A patent/KR101279244B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102152459A (en) * | 2009-12-23 | 2011-08-17 | 固特异轮胎和橡胶公司 | Continuous mixing system and apparatus |
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| JP5064701B2 (en) | 2012-10-31 |
| KR101279244B1 (en) | 2013-06-26 |
| JP2006291187A (en) | 2006-10-26 |
| WO2006098287A1 (en) | 2006-09-21 |
| CN101175794B (en) | 2011-02-09 |
| KR20070110940A (en) | 2007-11-20 |
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